To characterize the register of a secondary diagnosis of mental illnesses in all chronic obstructive pulmonary disease (COPD) hospitalizations registered in Portugal from 2008 to 2015 and explore their impact on hospitalization outcomes. A retrospective observational study was conducted. Hospitalizations of patients with at least 40 years old, discharged between 2008 and 2015 with a primary diagnosis of COPD (ICD-9-CM codes 491.x, 492.x and 496) were retrieved from a national administrative database. Comorbid psychiatric diagnoses were identified and defined by the HCUP Clinical Classification Software (CCS) category codes 650-670 (excluding 662). Length of hospital stay (LoS), admission type, in-hospital mortality, and estimated hospital charges were analyzed according to psychiatric diagnostic categories using sex and age-adjusted models. Of 66,661 COPD hospitalizations, 25,869 (38.8%) were episodes with a registered psychiatric comorbidity. These were more likely to correspond to younger inpatients (OR = 2.16, 95%CI 2.09-2.23; p < 0.001), to stay longer at the hospital (aOR = 1.08, 95%CI 1.05-1.12; p < 0.001), to incur in higher estimated hospital charges (aOR = 1.37, 95%CI 1.33-1.42; p < 0.001) and to be urgently admitted (aOR = 1.33, 95%CI 1.23-1.44; p < 0.001). After adjustment for age, in-hospital mortality was lower for episodes with psychiatric diagnoses (aOR = 0.90; 95%CI 0.84-0.96; p < 0.001), except for organic and neurodegenerative diseases category and developmental disorders, intellectual disabilities and disorders usually diagnosed in infancy, childhood, or adolescence category. These findings corroborate the additional burden placed by psychiatric disorders on COPD hospitalizations, highlighting the importance of individualizing care to address these comorbidities and minimize their impact on treatment outcomes.